Keratin fibre dye compositions containing pyrrolo-azole compounds, use thereof as couplers, and dyeing method

ABSTRACT

The present invention relates to a composition for the dyeing of keratinous fibres, especially human hair, which comprises, in a medium appropriate for dyeing:as coupler, at least one compound corresponding to one of the formulae:in which R1 is especially hydrogen, halogen, aryloxy, alkoxy, acyloxy, arylthio, alkylthio, heteroarylthio, heteroaryloxy, etc;R2 and R3 are independent and are especially hydrogen, halogen, alkyl, aryl, alkylthio, arylthio, benzylthio, etc;Za, Zb and Zc are independent and are a nitrogen atom or a carbon atom carrying a radical R4, R5, R6 or R7;R4, R6 and R7 are identical or different and are especially hydrogen, alkyl, aryl, a heterocycle, a halogen, etc; andR5 is especially hydrogen, halogen, acyl, acyloxy or carbamoyl, etc;and at least one oxidation base.

The invention relates to a composition for the dyeing of keratinousfibres, especially human hair, which comprises at least onepyrrolo-azole compound as coupler and at least one oxidation base.

It is known to dye keratinous fibres, and especially human hair, withdyeing compositions comprising oxidation dye precursors, especiallyortho- or para-phenylenediamines, ortho- or para-aminophenols andheterocyclic compounds, which are referred to generally as oxidationbases. The oxidation dye precursors, or oxidation bases, are colourlessor slightly coloured compounds which, when combined with oxidizingproducts, are able to give rise to coloured compounds and dyes by aprocess of oxidative condensation.

It is also known that the shades obtained with these oxidation bases canbe varied by combining them with couplers or coloration modifiers, thelatter being selected in particular from aromatic meta-diamines,meta-aminophenols, meta-diphenols and certain heterocyclic compounds,such as indole compounds.

The variety of molecules employed as oxidation bases and couplers makesit possible to obtain a wide range of colours.

The “permanent” coloration obtained by means of these oxidation dyes isrequired, moreover, to meet a certain number of requirements. Hence itmust have no toxicological drawbacks, must allow shades of the desiredintensity to be obtained, and must have good resistance to externalagents (light, inclement weather, washing, permanent-waving,perspiration and friction).

The dyes must also allow white hair to be covered and, finally, theymust be as unselective as possible; in other words, they must allow thesmallest possible differences in coloration to be produced over theentire length of a single keratinous fibre, which may in fact besensitized (i.e. damaged) differently between its tip and its root.

The Applicant has now discovered that it is possible to obtain new,powerful dyes, of low selectivity and particularly high resistance,which are capable of giving rise to intense colorations in variousshades, using pyrrolo-azole compounds as couplers in the presence of anoxidation base.

It is this discovery which forms the basis of the present invention.

The invention provides a composition for the dyeing of keratinous fibresand, in particular, of human keratinous fibres, such as hair, which ischaracterized in that it comprises, in a medium appropriate for dyeing:

as coupler, at least one pyrrolo-azole compound corresponding to one ofthe following formulae (I) and (II), or one of its addition salts withan acid:

in which:

R₁ is: a hydrogen atom; a halogen atom such as bromine, chlorine orfluorine; an acetylamido group; an alkoxy radical (such as, for example:methoxy, ethoxy, propyloxy, benzyloxy, methoxyethoxy, phenoxyethoxy,2-cyanoethoxy, phenethyloxy, p-chlorobenzyloxy ormethoxyethylcarbamoylmethoxy); an aryloxy radical (such as, for example:phenoxy, 4-methoxyphenoxy, 4-nitrophenoxy, 4-cyanophenoxy,4-methanesulphonamidophenoxy, 4-methanesulphonylphenoxy, 3-methylphenoxyor 1-naphthyloxy); an acyloxy radical (such as, for example: acetoxy,propanoyloxy, benzoyloxy, 2,4-dichlorobenzoyloxy, ethoxyalkyloxy,pyruvyloyloxy, cinnamoyloxy or myristoyloxy); an arylthio radical (suchas, for example: phenylthio, 4-carboxyphenylthio,2-ethoxy-5-tert-butylphenylthio, 2-carboxyphenylthio or4-methanesulphonylphenylthio); an alkylthio radical (such as, forexample: methylthio, ethylthio, propylthio, butylthio, 2-cyanoethylthio,benzylthio, phenethylthio, 2-(diethylamino)ethylthio, ethoxyethylthio orphenoxyethylthio); a heteroarylthio radical (such as, for example:5-phenyl-2,3,4,5-tetrazolylthio, 2-benzothiazolylthio); a heteroaryloxyradical (such as, for example: 5-phenyl-2,3,4,5-tetrazolyloxy or2-benzothiazolyloxy); a thiocyano radical; anN,N-diethylthiocarbonylthio radical; a dodecyloxythiocarbonylthioradical; a benzenesulphonamido radical; an N-ethyltoluenesulphonamidoradical; a pentafluorobutanamido radical; a2,3,4,5,6-pentafluorobenzamido radical; a p-cyanophenylureido radical;an N,N-diethylsulphamoylamino radical; a pyrazolyl radical; animidazolyl radical; a triazolyl radical; a tetrazolyl radical; abenzimidazolyl radical; a 1-benzyl-5-ethoxy-3-hydantoinyl radical; a1-benzyl-3-hydantoinyl radical; 5,5-dimethyl-2,4-dioxo-3-oxazolidinyl; a2-oxy-1,2-dihydro-1-pyridinyl radical; an alkylamido; an arylamido; aradical NR^(III)R^(IV) where R^(III) and R^(IV) are identical ordifferent and are a C₁-C₄ alkyl; a hydroxyalkyl; a carboxyl; or analkoxycarboxyl radical;

R₂ and R₃ are independently of one another a hydrogen atom; a halogenatom (such as bromine, chlorine or fluorine); a linear or branched C₁-C₅alkyl radical which is optionally substituted by one or two halogen,hydroxyl, alkoxy, aryloxy, amino, alkylamino, acyl or acylaminoradicals; a C₁-C₄ alkoxy radical; a C₁-C₄ alkylthio radical; an arylthioradical; a benzylthio radical; an acyl radical (such as acetyl,3-phenylpropanoyl, benzoyl or 4-dodecyloxybenzoyl); an acylaminoradical; an acyloxy radical (such as acetoxy); a carbamoyl radical (suchas carbamoyl, N-ethylcarbamoyl, N-phenylcarbamoyl, N,N-dibutylcarbamoylor N-(2-dodecyloxyethyl)carbamoyl); a phenyl radical which is optionallysubstituted by one or two halogen, nitro, sulphonyl, C₁-C₄ alkoxy, C₁-C₄alkyl, C₁-C₃ trifluoroalkyl, amino or alkylamino groups; analkoxycarbonyl radical (such as methoxycarbonyl, ethoxycarbonyl,isopropyloxycarbonyl, tert-butyloxycarbonyl, isobutyloxycarbonyl,butylcarbamoylethoxycarbonyl or perfluorohexylethoxycarbonyl); anaryloxycarbonyl radical (such as phenoxycarbonyl or2,5-diamylphenoxycarbonyl); a cyano radical; a nitro radical; adialkylphosphono radical (such as dimethylphosphono); a diarylphosphonoradical (such as diphenylphosphono); a dialkoxyphospholyl radical (suchas dimethoxyphospholyl); a dialkylphosphinyl radical (such asdimethylphosphinyl); a diarylphosphinyl radical (such asdiphenylphosphinyl); an alkylsulphinyl radical (such as3-phenoxypropylsulphinyl); an arylsulphinyl radical (such as3-phenoxypropylsulphinyl); an arylsulphonyl radical (such asbenzenesulphonyl or toluenesulphonyl); an alkylsulphonyl radical(methanesulphonyl, octanesulphonyl); a sulphonyloxy radical (such asmethanesulphonyloxy or toluenesulphonyloxy); an acylthio radical (suchas acetylthio or benzoylthio); a sulphamoyl radical (such asN-ethylsulphamoyl, N,N-diisopropylsulphamoyl or N,N-diethylsulphamoyl);a thiocyanate radical; or a thiocarbonyl radical (such asmethylthiocarbonyl or phenylthiocarbonyl);

Z_(a), Z_(b) and Z_(c) are independently of one another a nitrogen atomor a carbon atom carrying a radical R₄, R₅, R₆ or R₇;

R₄, R₆ and R₇ are identical or different and are a hydrogen atom; alinear or branched C₁-C₂₀ alkyl radical which is optionally substitutedby 1 or 2 radicals R selected from the group consisting of halogen,nitro, cyano, hydroxyl, alkoxy, aryloxy, amino, alkylamino, acylamino,carbamoyl, sulphonamido, sulphamoyl, imido, alkylthio, arylthio, aryl,alkoxycarbonyl and acyl; an aryl radical (such as phenyl or naphthyl)which is optionally substituted by 1 or 2 radicals R as defined above; a5- or 6-membered heterocycle having at least one nitrogen, oxygen orsulphur atom (such as pyridyl, quinolyl, pyrrolyl, morpholyl, furyl,tetrahydrofuryl, pyrazolyl, triazolyl, tetrazolyl, thiazolyl, oxazolyl,imidazolyl or thiadiazolyl) and being optionally substituted by 1 or 2radicals R as defined above;

when R₄, R₆ and R₇ are an alkyl radical, an aryl radical or a 5- or6-membered heterocycle (defined above), the radical or heterocycle maybe attached to the carbon atom of the ring system via an oxygen,nitrogen or sulphur atom (in this case, R₄, R₆ and R₇ become XR₄, XR₆ orXR₇ where X=O, NH, S);

R₄, R₆ and R₇ may also be a halogen atom (such as bromine, chlorine orfluorine); an acyl radical; a sulphonyl radical; a sulphinyl radical; aphosphonyl radical; a carbamoyl radical; a sulphamoyl radical; a cyanoradical; a siloxy radical; an amino radical; an acylamino radical; anacyloxy radical; a carbamoyloxy radical; a sulphonamide radical; animide radical; a ureido radical; a sulphamoylamino radical; analkoxycarbonylamino radical; an aryloxycarbonylamino radical; analkoxycarbonyl radical; an aryloxycarbonyl radical; or a carboxylradical;

R₅ is hydrogen; halogen; an acyl radical; an acyloxy radical; acarbamoyl radical; an alkoxycarbonyl radical; a cyano radical; a nitroradical; a dialkylphosphono radical; a diarylphosphono radical; adialkoxyphospholyl radical; a dialkylphosphinyl radical; adiarylphosphinyl radical; an alkylsulphinyl radical; an arylsulphinylradical; an alkylsulphonyl radical; an arylsulphonyl radical; asulphonyloxy radical; an acylthio radical; a sulphamoyl radical; athiocyanate radical; a thiocarbonyl radical; a haloaryloxy radical (suchas pentafluorophenyloxy); a haloalkylamino (such asN,N-di(trifluoromethylamino)); a haloalkylthio (such asdifluoromethylthio); an aryl which is unsubstituted or substituted byelectron-withdrawing groups (for example Cl, NO₂, F); or a heterocycle(such as 2-benzoxazolyl, 2-benzothiazolyl, pyrazolyl,5-chloro-1-tetrazolyl or 1-pyrrolyl);

and at least one oxidation base.

Among the radicals R₁ of formulae (I) and (II) preference is given toradicals selected from the group consisting of:

a hydrogen atom; a C₁-C₄ alkoxy; phenoxy; phenoxy substituted by ahalogen atom, a C₁-C₄ alkyl, a carboxyl or a trifluoromethyl group; anacyloxy radical; benzyloxy; C₁-C₄ alkylthio; phenylthio; phenylthiosubstituted by a halogen atom, a C₁-C₄ alkyl, a carboxyl or atrifluoromethyl group; a C₁-C₄ alkylamido; phenylamido; a radicalNR^(III)R^(IV) where R^(II) and R^(IV) are identical or different andare a C₁-C₄ alkyl, a C₁-C₄ hydroxyalkyl; a carboxyl or a C₁-C₄alkoxycarboxyl radical.

Among the radicals R₁ of the formulae (I) and (II) defined above,particular preference is given to radicals selected from the groupconsisting of:

hydrogen; chlorine or bromine; methoxy or ethoxy; phenyloxy;4-methylphenyloxy; acyloxy; benzyloxy; methylthio or ethylthio;phenylthio; 4-methylphenylthio; 2-tert-butylphenylthio; acetamido;phenylacetamido; dimethylamino; diethylamino; ethylmethylamino; and(β-hydroxyethyl)methylamino.

In addition, very particular preference is given to radicals R₁ selectedfrom the group consisting of: hydrogen; chlorine; ethoxy; phenoxy;benzyloxy; acyloxy; acetamido; and dimethylamino.

Among the radicals R₂ and R₃ of the formulae (I) and (II), preference isgiven to radicals selected from the group consisting of:

acyl; acyloxy; carbamoyl; alkoxycarbonyl; aryloxycarbonyl; cyano; nitro;alkylsulphinyl; arylsulphinyl; alkylsulphonyl; arylsulphonyl;sulphamoyl; haloalkyl; C₁-C₄ alkyl; and hydrogen.

Among the radicals R₂ and R₃ of the formulae (I) and (II) defined above,particular preference is given to radicals selected from the groupconsisting of:

acyl (such as acetyl, ethylcarbonyl or phenylcarbonyl); alkoxycarbonyl(such as methoxy- or ethoxycarbonyl); nitro; cyano; arylsulphonyl (suchas phenylsulphonyl); carbamoyl (such as carbamoyl or N-ethylcarbamoyl);haloalkyl (such as trifluoromethyl); hydrogen; and C₁-C₄ alkyl (such asmethyl or ethyl).

In addition, very particular preference is given to radicals R₂ selectedfrom the group consisting of: cyano; hydrogen; methyl; and phenyl, andto the radicals R₃ selected from the group consisting of:alkoxycarbonyl, such as methoxycarbonyl or ethoxycarbonyl;aryloxycarbonyl; hydrogen; methyl; and cyano.

Among the radicals R₄, R₆ and R₇ of the formulae (I) and (II),preference is given to radicals selected from the group consisting of:

a linear or branched C₁-C₄ alkyl radical; aryl, such as phenyl; phenylsubstituted by a halogen, a methoxy radical, a nitro group, a cyanogroup, a trifluoromethyl group or an amino group; cyano; nitro;acylamino; arylamino; alkylthio, such as methylthio or ethylthio;arylthio, such as phenylthio; carbamoyl, such as carbamoyl orN-ethylcarbamoyl; sulphonyl, such as methylsulphonyl; alkoxycarbonyl,such as methoxycarbonyl or ethyloxycarbonyl; aryloxycarbonyl, such asphenoxycarbonyl; acyl, such as acetyl or ethylcarbonyl; and hydrogen.

Additionally, very particular preference is given to the radicals R₄, R₆and R₇ of the formulae (I) and (II) selected from the group consistingof:

hydrogen; linear or branched C₁-C₄ alkyl (such as methyl, ethyl orisopropyl); aryl, such as phenyl; and phenyl substituted by a halogen, amethoxy radical, a nitro group, a cyano group, a trifluoromethyl groupor an amino group.

Among the radicals R₅ of the formulae (I) and (II) defined above,particular preference is given to radicals selected from the groupconsisting of:

acyl (such as acetyl, benzoyl or ethylcarbonyl); alkoxycarbonyl (such asmethoxy- or ethoxycarbonyl or isopropoxycarbonyl); aryloxycarbonyl suchas phenoxycarbonyl; nitro; cyano; arylsulphonyl (such asphenylsulphonyl); haloalkyl (such as trifluoromethyl); and a hydrogen.

Additionally, very particular preference is given to the radicals R₅selected from the group consisting of: cyano; alkoxycarbonyl (such asmethoxy- or ethoxycarbonyl); aryloxycarbonyl, such as phenoxycarbonyl;haloalkyl (such as trifluoromethyl); and a hydrogen.

Among the preferred compounds of the invention corresponding to theformula (I), mention may be made of those selected from the groupconsisting of:

(i) the pyrrolo[1,2-b]-1,2,4-triazoles of formula:

(ii) the pyrrolo[2,1-c]-1,2,4-triazoles of formula:

in which R₁, R₂, R₃ and R₄ are as defined above.

As examples of compounds of formula (Ia), particular mention may be madeof those for which:

R₁ is hydrogen or chlorine;

R₂ and R₃ are, respectively: cyano and cyano; ethyloxycarbonyl andcyano; trifluoromethyl and cyano; phenylsulphonyl and cyano;trifluoromethyl and ethyloxycarbonyl; ethyloxycarbonyl andethyloxycarbonyl; methyloxycarbonyl and methyloxycarbonyl; hydrogen andhydrogen; or hydrogen and methyl; and

R₄ is methyl, ethyl, isopropyl, phenyl or hydrogen.

Among the compounds of formula (Ia) above, very particular mention maybe made of:

3,4-dicyano-8-methylpyrrolo[1,2-b]-1,2,4-triazole,

3,4-dicyano-8-phenylpyrrolo[1,2-b]-1,2,4-triazole,

3,4-dicyano-8-tert-butylpyrrolo[1,2-b]-1,2,4-triazole,

5-chloro-3,4-dicyano-8-methylpyrrolo[1,2-b]-1,2,4-triazole,

and their addition salts with an acid.

As examples of compounds of formula (Ib) particular mention may be madeof those for which:

R₁ is hydrogen or chlorine;

R₂ and R₃ are simultaneously cyano or hydrogen; and

R₄ is methyl, ethyl, isopropyl, phenyl or hydrogen.

Among the compounds of formula (Ib) above, very particular mention maybe made of:

5,6-dicyano-3-methylpyrrolo[2,1-c]-1,2,4-triazole,

7-chloro-5,6-dicyano-3-methylpyrrolo[2,1-c]-1,2,4-triazole,

and their addition salts with an acid.

Among the preferred compounds of the invention corresponding to formula(II), mention may be made of those selected from the group consistingof:

a) the pyrrolo[1,2-b]-1,2,4-triazoles of formula:

b) the pyrrolo[2,1-c]-1,2,4-triazoles of formula:

c) the pyrrolo[1,2-c]imidazoles of formula:

d) the pyrrolo[1,2-e]tetrazoles of formula:

e) the pyrrolo[1,2-a]pyrroles of formula:

f) the pyrrolo[1,2-a]imidazoles of formula:

g) the pyrrolo[1,2-c]-1,2,3-triazoles of formula:

in which R₄, R₅, R₆ and R₇ are as defined above.

As examples of compounds of formula (IIa), mention may be made inparticular of those for which:

R₁ is hydrogen or chlorine;

R₂ and R₃ are, respectively: methoxycarbonyl and cyano; ethyloxycarbonyland cyano; cyano and methoxycarbonyl or ethoxycarbonyl; cyano andtrifluoromethyl; cyano and phenylsulphonyl; methyloxycarbonyl andmethyloxycarbonyl; hydrogen and hydrogen; hydrogen and methyl;trifluoromethyl and cyano or trifluoromethyl and methyloxycarbonyl;carboxyl and cyano; cyano and cyano; ethyloxycarbonyl andethyloxycarbonyl; phenyl and cyano; methyl and hydrogen; and

R₄ is methyl, ethyl, isopropyl, phenyl or hydrogen.

Among the compounds of formula (IIa) above, very particular mention maybe made of:

5-cyano-4-ethoxycarbonyl-8-methylpyrrolo[1,2-b]-1,2,4-triazole,

5-cyano-4-carboxy-8-methylpyrrolo[1,2-b]-1,2,4-triazole,

4,5-dicyano-8-methylpyrrolo[1,2-b]-1,2,4-triazole,

5-cyano-8-methyl-4-phenylpyrrolo[1,2-b]-1,2,4-triazole,

4,8-dimethylpyrrolo[1,2-b]-1,2,4-triazole,

4,5-di(ethyloxycarbonyl)-8-methylpyrrolo[1,2-b]-1,2,4-triazole,

3-chloro-5-cyano-4-ethoxycarbonyl-8-methylpyrrolo-[1,2-b]-1,2,4-triazole,

5-cyano-4-ethoxycarbonyl-8-phenylpyrrolo[1,2-b]-1,2,4-triazole,

5-cyano-4-carboxy-8-phenylpyrrolo[1,2-b]-1,2,4-triazole,

4,5-dicyano-8-phenylpyrrolo[1,2-b]-1,2,4-triazole,

4,5-di(ethyloxycarbonyl)-8-phenylpyrrolo[1,2-b]-1,2,4-triazole,

3-chloro-5-cyano-4-ethoxycarbonyl-8-phenylpyrrolo-[1,2-b]-1,2,4-triazole,

4-cyano-5-carboxy-8-(2-nitro-5-hydroxyphenyl)pyrrolo-[1,2-b]-1,2,4-triazole,and their addition salts with an acid.

As examples of compounds of formula (IIb), mention may be made inparticular of those for which:

R₁ is hydrogen or chlorine;

R₂ and R₃ are, respectively: cyano and methoxycarbonyl; methoxycarbonyland cyano; methoxycarbonyl and methoxycarbonyl; hydrogen and hydrogen orhydrogen and methyl; cyano and cyano; ethyloxycarbonyl andethyloxycarbonyl; phenyl and cyano; tert-butyl and cyano; and

R₄ is methyl, ethyl, isopropyl, phenyl or hydrogen.

Among the compounds of formula (IIb) above, very particular mention maybe made of:

6,7-dicyano-3-methylpyrrolo[2,1-c]-1,2,4-triazole,

5-chloro-6,7-dicyano-3-methylpyrrolo[2,1-c]-1,2,4-triazole,

6,7-di (ethyloxycarbonyl)-3-methylpyrrolo [2,1-c]-1,2,4-triazole,

7-cyano-3-methyl-6-phenylpyrrolo[2,1-c]-1,2,4-triazole,

7-cyano-3-methyl-6-tert-butylpyrrolo[2,1-c]-1,2,4-triazole,

and their addition salts with an acid.

As examples of compounds of formula (IIc), particular mention may bemade of those for which:

R₁ is acetamido, chlorine or hydrogen;

R₂ and R₃ are, respectively: methoxycarbonyl and cyano; or cyano andcyano;

R₄ is hydrogen; and

R₅ is cyano.

Among the compounds of the formula (IIc) above, very particular mentionmay be made of:

6,8-dicyano-5-ethoxycarbonylpyrrolo [1,2-c]imidazole,

4-chloro-6,8-dicyano-5-ethoxycarbonylpyrrolo[1,2-c]-imidazole,

and their addition salts with an acid.

As examples of compounds of formula (IId), particular mention may bemade of those for which:

R₁ is hydrogen or chlorine; and

R₂ and R₃ are, respectively: cyano and methoxycarbonyl; cyano and cyano;methoxycarbonyl and cyano; methoxycarbonyl and methoxycarbonyl; hydrogenand hydrogen or hydrogen and methyl.

Among the compounds of formula (IId) above, very particular mention maybe made of:

6,7-dicyanopyrrolo[1,2-e]tetrazole,

6-cyano-7-ethoxycarbonylpyrrolo[1,2-e]tetrazole,

5-chloro-6,7-dicyanopyrrolo[1,2-e]tetrazole,

and their addition salts with an acid.

As examples of compounds of formula (IIe), particular mention may bemade of those for which:

R₁ is hydrogen or chlorine;

R₂ and R₃ are, respectively: cyano and methoxycarbonyl;

R₅ is trifluoromethyl;

R₆ is phenyl or methyl; and

R₇ is methyl.

As examples of compounds of formula (IIf), particular mention may bemade of those for which:

R₁ is hydrogen or chlorine; and

R₂, R₃, R₆ and R₇ are, respectively:

methoxycarbonyl/cyano/cyano/phenyl;

cyano/methoxycarbonyl/cyano/phenyl;

cyano/methoxycarbonyl/methoxycarbonyl/phenyl;

hydrogen/hydrogen/hydrogen/hydrogen; or

hydrogen/hydrogen/methyl/methyl.

Among the compounds of formula (IIf) above, very particular mention maybe made of:

2,3,7-tricyano-6-methylpyrrolo[1,2-a]imidazole,

2,3,7-tricyano-6-trifluoromethylpyrrolo[1,2-a]-imidazole,

2,3,7-tricyano-6-tert-butylpyrrolo[1,2-a]imidazole,

2,3,7-tricyano-6-phenylpyrrolo[1,2-a]imidazole,

2,3,7-tricyano-6-ethoxycarbonylpyrrolo[1,2-a]-imidazole,

5-chloro-2,3,7-tricyano-6-tert-butylpyrrolo[1,2-a]-imidazole,

5-chloro-2,3,7-tricyano-6phenylpyrrolo[1,2-a]-imidazole,

7-cyano-6-pethoxycarbonylpyrrolo[1,2-a]benzimidazole,

7-cyano-6-phenylpyrrolo[1,2-a]benzimidazole,

7-amido-6-ethoxycarbonylpyrrolo[1,2-a]benzimidazole,

and their addition salts with an acid.

As examples of compounds of formula (IIg), particular mention may bemade of those for which:

R₁ is hydrogen or chlorine;

R₂ is cyano;

R₃ is methoxycarbonyl; or ethyloxycarbonyl; and

R₅ is cyano.

Among the compounds of formula (IIg) above, very particular mention maybe made of:

5,6,8-tricyanopyrrolo[1,2-c]-1,2,3-triazole,

5,8-dicyano-6-ethoxycarbonylpyrrolo[1,2-c]-1,2,3-triazole,

4-chloro-5,8-dicyano-6-ethoxycarbonylpyrrolo[1,2-c]-1,2,3-triazole,

and their addition salts with an acid.

The acid addition salts of the compounds of the invention can beselected in particular from hydrochlorides, hydrobromides, tartrates,tosylates, benzenesulphonates, sulphates, lactates and acetates.

The compounds of the present invention, their synthesis intermediatesand the processes for their preparation are described in the patents andpatent applications U.S. Pat. No. 5,256,526, EP-A-557 851, EP-A-578 248,EP-A-518 238, EP-A-456 226, EP-A-488 909, EP-A-488 248 and in thefollowing publications:

D. R. Liljegren, Ber. 1964, 3436;

E. J. Browne, J.C.S., 1962, 5149;

P. Magnus, J.A.C.S., 1990, 112, 2465;

P. Magnus, J.A.C.S., 1987, 109, 2711;

Angew. Chem. 1960, 72, 956;

and Rec. Trav. Chim. 1961, 80, 1075.

The compound or compounds of formula (I) or (II) make up preferablybetween 0.0005 and 12% by weight, approximately, of the total weight ofthe dyeing composition and, more particularly, between 0.005 and 6% byweight.

The nature of the oxidation base or bases which can be employed in thedyeing composition according to the invention is not critical. This orthese oxidation base or bases are preferably selected frompara-phenylenediamines, bisphenylalkylenediamines, para-aminophenols,ortho-aminophenols, heterocyclic bases, and their addition salts with anacid.

Among the para-phenylenediamines which can be employed as oxidationbases in the dyeing composition according to the invention, particularmention may be made of the compounds corresponding to the followingformula (III) and their addition salts with an acid:

in which:

R₈ is a hydrogen atom or a C₁-C₄ alkyl, C₁-C₄ monohydroxyalkyl, C₂-C₄polyhydroxyalkyl or C₁-C₄-alkoxy-C₁-C₄-alkyl radical,

R₉ is a hydrogen atom or a C₁-C₄ alkyl, C₁-C₄ monohydroxyalkyl or C₂-C₄polyhydroxyalkyl radical,

R₁₀ is a hydrogen atom, a halogen atom, such as a chlorine atom, or aC₁-C₄ alkyl, sulpho, carboxyl, C₁-C₄ monohydroxyalkyl or C₁-C₄hydroxyalkoxy radical, and

R₁₁ is a hydrogen atom or a C₁-C₄ alkyl radical.

In the formula (III) above, and when R₁₀ is other than a hydrogen atom,R₈ and R₉ are preferably a hydrogen atom and R₁₀ is preferably the sameas R₁₁, and, when R₁₀ is a halogen atom, R₈, R₉ and R₁₀ are preferably ahydrogen atom.

Among the para-phenylenediamines of the formula (III) above, moreparticular mention may be made of para-phenylenediamine,para-tolylenediamine, 2-isopropyl-para-phenylenediamine,2-β-hydroxyethylpara-phenylenediamine,2-β-hydroxyethyloxy-paraphenylenediamine,2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine,2,3-dimethyl-para-phenylenediamine,N,N-bis(β-hydroxyethyl)-paraphenylenediamine,4-amino-1-(β-methoxyethyl)amino-benzene and2-chloro-para-phenylenediamine, and their addition salts with an acid.

Among the bisphenylalkylenediamines which can be employed as oxidationbases in the dyeing composition according to the invention, particularmention may be made of the compounds corresponding to the followingformula (IV) and their addition salts with an acid:

in which:

Q₁ and Q₂ are identical or different and are a hydroxyl radical or aradical NHR₁₅ in which R₁₅ is a hydrogen atom or a C₁-C₄ alkyl radical,

R₁₂ is a hydrogen atom or a C₁-C₄ alkyl, C₁-C₄ monohydroxyalkyl or C₂-C₄polyhydroxyalkyl radical or a C₁-C₄ aminoalkyl radical whose aminomoiety may be substituted,

R₁₃ and R₁₄ are identical or different and are a hydrogen or halogenatom or a C₁-C₄ alkyl radical,

W is a radical taken from the group consisting of the followingradicals:

in which n is an integer from 0 to 8 inclusive and m is an integer from0 to 4 inclusive.

Among the bisphenylalkylenediamines of formula (IV) above, moreparticular mention may be made ofN,N′-bis(β-hydroxyethyl)-N,N′-bis(4′-aminophenyl)-1,3-diamino-2-propanol,N,N′-bis(β-hydroxyethyl)-N,N′-bis(4′-aminophenyl)ethylenediamine,N,N′-bis(4-aminophenyl)tetramethylenediamine,N,N′-bis(β-hydroxyethyl)-N,N′-bis(4-aminophenyl)tetramethylenediamine,N, N′-bis(4-methylaminophenyl)tetramethylenediamine andN,N′-bis(ethyl)-N,N′-bis(4′-amino-3′-methylphenyl)ethylenediamine, andtheir addition salts with an acid.

Among these bisphenylalkylenediamines of formula (IV),N,N′-bis(β-hydroxyethyl)-N,N′-bis-(4′-aminophenyl)-1,3-diaminopropanol,or one of its addition salts with an acid, are particularly preferred.

Among the para-aminophenols which can be employed as oxidation bases inthe dyeing composition according to the invention, particular mentionmay be made of the compounds corresponding to the following formula (V)and their addition salts with an acid:

in which:

R₁₆ is a hydrogen atom or a C₁-C₄ alkyl, C₁-C₄ monohydroxyalkyl,C_(l)-C₄-alkoxy-C₁-C₄-alkyl or C₁-C₄ aminoalkyl radical, and

R₁₇ is a hydrogen or fluorine atom or a C₁-C₄ alkyl, C₁-C₄monohydroxyalkyl, C₂-C₄ polyhydroxyalkyl, C₁-C₄ aminoalkyl, C₁-C₄cyanoalkyl or C₁-C₄-alkoxy-C₁-C₄-alkyl radical,

it being understood that at least one of the radicals R₁₆ and R₁₇ is ahydrogen atom.

Among the para-aminophenols of formula (V) above, more particularmention may be made of para-aminophenol, 4-amino-3-methylphenol,4-amino-3-fluorophenol, 4-amino-3-hydroxymethylphenol,4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol,4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol and4-amino-2-(β-hydroxyethylaminomethyl)phenol, and their addition saltswith an acid.

Among the ortho-aminophenols which can be employed as oxidation bases inthe dyeing composition according to the invention, particular mentionmay be made of 2-aminophenol, 2-amino-1-hydroxy-5-methylbenzene,2-amino-1-hydroxy-6-methylbenzene, and 5-acetamido-2-aminophenol, andtheir addition salts with an acid.

Among the heterocyclic bases which can be employed as oxidation bases inthe dyeing composition according to the invention, particular mentionmay be made of pyridine derivatives, pyrimidine derivatives, andpyrazole derivatives, and their addition salts with an acid.

Among pyridine derivatives more particular mention may be made of thecompounds described, for example, in the patents GB 1 026 978 and GB 1153 196, such as 2,5-diaminopyridine, and their addition salts with anacid.

Among pyrimidine derivatives more particular mention may be made of thecompounds described, for example, in the German patent DE 2 359 399 orJapanese patents JP 88-571 and JP 91-333 495, such as2,4,5,6-tetraaminopyrimidine and 4-hydroxy-2,5,6-triaminopyrimidine, andtheir addition salts with an acid.

Among pyrazole derivatives more particular mention may be made of thecompounds described in the patents DE 3 843 892 and DE 4 133 957 andpatent applications WO 94/08969 and WO 94/08970, such as4,5-diamino-1-methylpyrazole, 3,4-diaminopyrazole and1-(4′-chlorobenzyl)-4,5-diaminopyrazole, and their addition salts withan acid.

According to the invention, the oxidation base or bases make uppreferably from 0.0005 to 12% by weight, approximately, of the totalweight of the dyeing composition, and more preferably still from 0.005to 6% by weight, approximately, of this weight.

The dyeing composition according to the invention may also include oneor more additional couplers other than the compounds of formula (I)and/or one or more direct dyes, so as to vary or enrich in glints theshades obtained with the oxidation bases.

The additional couplers which can be employed in the compositionaccording to the invention may be selected from the couplers employedconventionally in oxidation dyeing, among which particular mention maybe made of meta-phenylenediamines, meta-aminophenols, meta-diphenols andheterocyclic couplers such as, for example, indole derivatives andindoline derivatives, and their addition salts with an acid.

These couplers may be selected in particular from2-methyl-5-aminophenol, 5-N-(β-hydroxyethyl)amino-2-methylphenol,3-aminophenol, 1,3-dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene,4-chloro-1,3-dihydroxybenzene, 2,4-diamino-1-(β-hydroxyethyloxy)benzene,2-amino-4-(β-hydroxyethylamino)-1-methoxybenzene, 1,3-diaminobenzene,1,3-bis(2,4-diaminophenoxy)propane, sesamol, α-naphthol,6-hydroxyindole, 4-hydroxyindole, 4-hydroxy-N-methylindole and6-hydroxyindoline, and their addition salts with an acid.

When present, these additional couplers make up preferably from 0.0005to 5% by weight, approximately, of the total weight of the dyeingcomposition, and more preferably still from 0.005 to 3% by weight,approximately, of this weight.

The acid addition salts of the oxidation base or bases and/or of theadditional couplers which can be employed in the dyeing composition ofthe invention are selected in particular from hydrochlorides,hydrobromides, sulphates and tartrates, lactates and acetates.

The medium appropriate for dyeing (or vehicle) consists generally ofwater or of a mixture of water and at least one organic solvent forsolubilizing the compounds which would not be sufficiently soluble inwater. As organic solvent mention may be made, for example, of C₁-C₄lower alkanols, such as ethanol and isopropanol; glycerol; glycols andglycol ethers, such as 2-butoxyethanol, propylene glycol, propyleneglycol monomethyl ether, diethylene glycol monoethyl ether andmonomethyl ether, and aromatic alcohols, such as benzyl alcohol orphenoxyethanol, similar products, and mixtures thereof.

The solvents can be present in proportions of preferably between 1 and40% by weight, approximately, relative to the total weight of the dyeingcomposition, and more preferably still between 5 and 30% by weight,approximately.

The pH of the dyeing composition according to the invention is generallybetween 3 and 12. It can be adjusted to the desired value usingacidifying or basifying agents commonly employed in dyeing keratinousfibres.

Among the acidifying agents mention may be made, by way of example, ofmineral or organic acids, such as hydrochloric acid, orthophosphoricacid, carboxylic acids, such as tartaric acid, citric acid and lacticacid, and sulphonic acids.

Among the basifying agents mention may be made, by way of example, ofaqueous ammonia, alkali metal carbonates, alkanolamines such as mono-,di- and triethanolamines, and derivatives thereof, sodium hydroxide orpotassium hydroxide, and the compounds of the following formula (VI):

in which R is a propylene radical which is optionally substituted by ahydroxyl group or a C₁-C₄ alkyl radical; R₁₈, R₁₉, R₂₀ and R₂₁ areidentical or different and are a hydrogen atom or a C₁-C₄ alkyl or C₁-C₄hydroxyalkyl radical.

The dyeing composition according to the invention may also includevarious adjuvants conventionally employed in hair dye compositions, suchas anionic, cationic, nonionic, amphoteric and zwitterionic surfactantsor mixtures thereof, anionic, cationic, nonionic, amphoteric andzwitterionic polymers or mixtures thereof, organic or inorganicthickeners, antioxidants, penetration agents, sequestering agents,fragrances, buffers, dispersants, conditioners, such as silicones, forexample, film formers, preservatives and opacifiers.

The person skilled in the art will of course take care to select theabovementioned optional complementary compound(s) such that theadvantageous properties intrinsic to the dyeing composition according tothe invention are not, or not substantially, impaired by the intendedaddition(s).

The dyeing composition according to the invention may be in variousforms, such as in the form of liquids, creams or gels or any other formwhich is appropriate for dyeing keratinous fibres, and especially humanhair.

The invention also provides for the use of the compounds of formula (I)or (II) above, as coupler, in combination with at least one oxidationbase for the oxidation dyeing of keratinous fibres and, in particular,of human keratinous fibres such as hair.

The invention additionally provides a method of oxidation-dyeingkeratinous fibres, and especially human keratinous fibres such as hair,employing the dyeing composition as defined above.

In accordance with this method, at least one dyeing composition asdefined above is applied to the fibres, the colour being developed at anacidic, neutral or alkaline pH with the aid of an oxidizing agent whichis added just at the moment when the dyeing composition is employed orwhich is present in an oxidizing composition which is appliedsimultaneously or sequentially and separately.

According to a particularly preferred embodiment of the dyeing methodaccording to the invention, the above-described dyeing composition ismixed at the time of use with an oxidizing composition which comprises,in a medium appropriate for dyeing, at least one oxidizing agent presentin a quantity which is sufficient to develop a coloration. The resultingmixture is subsequently applied to the keratinous fibres and is left toact for from 3 to 50 minutes approximately, preferably from 5 to 30minutes approximately, after which the fibres are rinsed, shampooed,rinsed again and dried.

The oxidizing agent present in the oxidizing composition as definedabove may be selected from the oxidizing agents conventionally employedfor the oxidation dyeing of keratinous fibres, among which mention maybe made of hydrogen peroxide, urea peroxide, alkali metal bromates, andpersalts, such as perborates and persulphates. Hydrogen peroxide isparticularly preferred.

The pH of the oxidizing composition comprising the oxidizing agent asdefined above is such that, after it has been mixed with the dyeingcomposition, the pH of the resulting composition applied to thekeratinous fibres varies preferably between 3 and 12 approximately and,more preferably still, between 5 and 11. It is adjusted to the desiredvalue using acidifying or basifying agents which are commonly employedin dyeing keratinous fibres and are as defined above.

The oxidizing composition as defined above may also include variousadjuvants which are conventionally employed in hair dye compositions andare as defined above.

The composition which is ultimately applied to the keratinous fibres maybe in various forms, such as in the form of liquids, creams, gels or anyother form appropriate for dyeing keratinous fibres and, in particular,human hair.

The invention also provides a multi-compartment dyeing device or kit, orany other multi-compartment packaging system, a first compartment ofwhich contains the dyeing composition as defined above and a secondcompartment of which contains the oxidizing composition as definedabove. These devices can be equipped with a means permitting the desiredmixture to be delivered to the hair, such as the devices described inthe patent FR-2 586 913 in the name of the Applicant.

EXAMPLES Examples 1 and 2 Dyeing in an alkaline medium

The following dyeing compositions according to the invention wereprepared (contents in grams):

Example 1 2 5-cyano-4-ethoxycarbonyl-8-methyl- 0.654 0.654pyrrolo[1,2-b]-1,2,4-triazole (coupler) 4-amino-1-(β-methoxyethyl)amino-0.498 — benzene (oxidation base) 4,5-diamino-1,3-dimethylpyrazole —0.384 (oxidation base) Common dye vehicle No. 1 No. 1 Demineralizedwater q.s. 100 g 100 g

NB: 5-cyano-4-ethoxycarbonyl-8-methylpyrrolo[1,2-b]-1,2,4-triazole wasprepared by the process described in patent application EP-A-518 238.

Common Dye Vehicle No. 1:

Ethanol   20 g Aqueous ammonia containing 20% NH₃   10 g Sodiummetabisulphite 0.228 g

Sequestering agent q.s.

Each of the dyeing compositions of Examples 1 and 2 above was mixed atthe time of use with an equal weight of a 20-volumes hydrogen peroxidesolution (6% by weight).

Each of the resulting mixtures was applied for 30 minutes to locks ofnatural grey hair containing 90% white hairs, permed or otherwise, in anamount of 10 g per g of hair. After rinsing, washing with a standardshampoo and drying, the locks were dyed in the shades indicated in Table1 below:

TABLE 1 Shade obtained on Shade obtained on natural grey hair permedgrey hair pH of the containing 90% containing 90% Example mixture whitehairs white hairs 1 9.9 Bottle green Bottle green 2 9.9 Coppery yellowcoppery orange

EXAMPLES 3 to 6 Dyeing in a Neutral Medium

The following dyeing compositions according to the invention wereprepared (contents in grams):

Example 3 4 5 6 5-cyano-4-ethoxycarbonyl-8-methyl- 0.654 0.654 — —pyrrolo[1,2-b]-1,2,4-triazole (coupler)5-cyano-4-phenyl-8-methylpyrrolo- — — 0.666 — [1,2-b]-1,2,4-triazole(coupler) 7-amido-6-ethoxycarbonylpyrrolo- — — — 0.813[1,2-a]benzimidazole (coupler) 4-amino-1-(β-methoxyethyl)amino- 0.4980.498 0.498 0.498 benzene (oxidation base) Common dye vehicle No. 2 No.2 No. 2 No. 2 Demineralized water q.s. 100 g 100 g 100 g 100 g

NB: 5-cyano-4-phenyl-8-methylpyrrolo[1,2-b]-1,2,4-triazole was preparedby the process described in the patent U.S. Pat. No. 5,256,526 and7-amido-6-ethoxycarbonylpyrrolo[1,2-a]benzimidazole was prepared by theprocess described in the patent application Eβ-A-518 238.

Comon Dye Vehicle No. 2:

Ethanol 20.0 g

K₂HPO₄/KH₂PO₄ (1.5 M/1 M) buffer 10.0 g

Sodium metabisulphite 0.228 g

Sequestering agent q.s.

Each of the dyeing compositions of Examples 3 and 6 above was mixed atthe time of use with an equal weight of a 20-volumes hydrogen peroxidesolution (6% by weight).

Each of the dyeing compositions of Examples 4 and 5 above was mixed atthe time of use with an equal quantity by weight of a 6×10⁻³ mol-%aqueous ammonium persulphate solution.

Each of the resulting mixtures was applied for 30 minutes to locks ofnatural grey hair containing 90% white hairs, permed or otherwise, in anamount of 10 g per g of hair. After rinsing, washing with a standardshampoo and drying, the locks were dyed in the shades indicated in Table2 below:

TABLE 2 Shade obtained on Shade obtained on natural grey hair permedgrey hair pH of the containing 90% containing 90% Example mixture whitehairs white hairs 3 6.8 Green-bluish grey Green-bluish grey 4 6.8Blue-mauvish grey Blue-mauvish grey 5 6.8 Mauvish blue Mauvish blue 66.8 Blue-greenish grey Blue-greenish grey

What is claimed is:
 1. A process for oxidation-dyeing keratin fiberscomprising: (a) applying to the fibers an effective amount for dyeing ofat least one dyeing composition; (b) developing color at acidic,neutral, or alkaline pH in the presence of at least one oxidizing agentwhich is added to the dyeing composition at the time that the dyeingcomposition is applied, or which is present in an oxidizing compositionthat is applied: (i) separately from the dyeing composition at the sametime that the dyeing composition is applied to the fibres, or (ii)sequentially with the dyeing composition, wherein said at least onedyeing composition, comprises, in a medium which is suitable for dyeing:(a) a coupler, wherein said coupler is at least one pyrrolo-azolecompound corresponding to formulae (I) or (II), or an acid addition saltthereof:

wherein: R₁ is a hydrogen atom; a halogen atom; an acetylamido radical;an alkoxy radical; an aryloxy radical; an acyloxy radical; an arylthioradical; an alkylthio radical; a heteroarylthio radical; a heteroaryloxyradical; a thiocyano radical; an N,N-diethylthiocarbonylthio radical; adodecyloxythiocarbonylthio radical; a benzenesulphonamido radical; anN-ethyltoluenesulphonamido radical; a pentafluorobutanamido radical; a2,3,4,5,6-pentafluorobenzamido radical; a P-cyanophenylureido radical;an N,N-diethylsulphamoylamino radical; a pyrazolyl radical; animidazolyl radical; a triazolyl radical; a tetrazolyl radical; abenzimidazolyl radical; a 1-benzyl-5-ethoxy-3-hydantoinyl radical; a1-benzyl-3-hydantoinyl radical; 5,5-dimethyl-2,4-dioxo-3-oxazolidinyl; a2-oxy-1,2-dihydro-1-pyridinyl radical; an alkylamido; an arylamido;acetylamido; a radical NR^(III)R^(IV) wherein R^(III) and R^(IV) eachindependently are a C₁-C₄ alkyl or a hydroxyalkyl; a carboxyl; or analkoxycarbonyl radical; R₂ and R₃ each independently are a hydrogenatom; a halogen atom; a linear or branched C₁-C₅ alkyl radical which isunsubstituted or substituted by one or two halogen, hydroxyl, alkoxy,aryloxy, amino, alkylamino, acyl or acylamino radicals; a C₁-C₄ alkoxyradical; a C₁-C₄ alkylthio radical; an arylthio radical; a benzylthioradical; an acyl radical; an acylamino radical; an acyloxy radical; acarbamoyl radical; a phenyl radical which is unsubstituted orsubstituted by one or two halogen, nitro, sulphonyl, C₁-C₄ alkoxy, C₁-C₄alkyl, C₁-C₃ trifluoroalkyl, amino or alkylamino groups; analkoxycarbonyl radical; an aryloxycarbonyl radical; a cyano radical; anitro radical; a dialkylphosphono radical; a diarylphosphono radical; adialkoxyphospholyl radical; a dialkylphosphinyl radical; adiarylphosphinyl radical; an alkylsulphinyl radical; an arylsulphinylradical; an arylsulphonyl radical; an alkylsulphonyl radical; asulphonyloxy radical; an acylthio radical; a sulphamoyl radical; ahaloalkyl radical; a thiocyanate radical; or a thiocarbonyl radical;Z_(a), Z_(b) and Z_(c) each independently are a nitrogen atom or acarbon atom carrying a radical R₄, R₅, R₆ or R₇; R₄ R₆ and R₇ eachindependently are a hydrogen atom; a linear or branched C₁-C₂₀ alkylradical, unsubstituted or substituted by 1 or 2 radicals R, wherein R ishalogen, nitro, cyano, hydroxyl, alkoxy, aryloxy amino, alkylamino,acylamino, carbamoyl, sulphonamido, sulphamoyl, trifluoromethyl, imido,alkylthio, arylthio, aryl, alkoxycarbonyl or acyl; an aryl radical,unsubstituted or substituted by 1 or 2 radicals R as defined above; or a5- or 6-membered heterocycle having at least one nitrogen, oxygen orsulphur atom, unsubstituted or substituted by 1 or 2 radicals R asdefined above; with the proviso that when R₄, R₆ and R₇ are an alkylradical, an aryl radical or a 5- or 6-membered heterocycle, said radicalor said heterocycle may be attached to the carbon atom of the ringsystem via an oxygen, nitrogen or sulphur atom, such that R₄, R₆ and R₇are XR₄, XR₆ or XR₇, wherein X is an oxygen, nitrogen or sulphur atom;R₄, R₆ and R₇ may also each independently be a halogen atom; an acylradical; a sulphonyl radical; a sulphinyl radical; a phosphonyl radical;a carbamoyl radical; a sulphamoyl radical; a cyano radical; a nitroradical; a siloxy radical; alkylthio; arylthio; an amino radical; anacylamino radical; arylamino; an acyloxy radical; a carbamoyloxyradical; a sulphonamide radical; an imide radical; a ureido radical; asulphamoylamino radical; an alkoxycarbonylamino radical; anaryloxycarbonylamino radical; an alkoxycarbonyl radical; anaryloxycarbonyl radical; or a carboxyl radical; R₅ is hydrogen; halogen;an acyl radical; an acyloxy radical; a carbamoyl radical; analkoxycarbonyl radical; an aryloxycarbonyl radical; a cyano radical; anitro radical; a dialkylphosphono radical; a diarylphosphono radical; adialkoxyphospholyl radical; a dialkylphosphinyl radical; adiarylphosphinyl radical; an alkylsulphinyl radical; an arylsulphinylradical; an alkylsulphonyl radical; an arylsulphonyl radical; asulphonyloxy radical; an acylthio radical; a sulphamoyl radical; athiocyanate radical; a thiocarbonyl radical; a haloalkyl radical; ahaloaryloxy radical, a haloalkylamino radical, a haloalkylthio; an aryloptionally substituted by at least one electron-withdrawing group; or aheterocycle; and (b) at least one oxidation base or an addition saltthereof.
 2. A process according to claim 1, wherein said keratin fibersare human keratin fibers.
 3. A process according to claim 1, whereinsaid human keratin fibers are hair.
 4. A process according to claim 1,wherein R₁ is a hydrogen atom; a C₁-C₄ alkoxy; phenoxy; phenoxysubstituted by a halogen atom, a C₁-C₄ alkyl, a carboxyl group or atrifluoromethyl group; an acyloxy radical; benzyloxy; C₁-C₄ alkylthio;phenylthio; phenylthio substituted by a halogen atom, a C₁-C₄ alkyl, acarboxyl group or a trifluoromethyl group; a C₁-C₄ alkylamido;phenylamido; a radical NR^(III)R^(IV), wherein R^(III) and R^(IV)independently are selected from a C₁-C₄ alkyl and a C₁-C₄ hydroxyalkyl;a carboxyl; or a C₁-C₄ alkoxycarboxyl radical.
 5. A process according toclaim 1, wherein R₁ is hydrogen; chlorine; bromine; methoxy; ethoxy;phenyloxy; 4-methylphenyloxy; acyloxy; benzyloxy; methylthio; ethylthio;phenylthio; 4-methylphenylthio; 2-tert-butylphenylthio; acetamido;phenylacetamido; dimethylamino; diethylamino; ethylmethylamino; or(β-hydroxyethyl)methylamino.
 6. A process according to claim 5, whereinR₁ is hydrogen; chlorine; ethoxy; phenoxy; benzyloxy; acyloxy;acetamido; or dimethylamino.
 7. A process according to claim 1, whereinR₂ and R₃ are each independently acyl; acyloxy; carbamoyl;alkoxycarbonyl; aryloxycarbonyl; cyano; nitro; alkylsulphinyl;arylsulphinyl; alkylsulphonyl; arylsulphonyl; sulphamoyl; haloalkyl;C₁-C₄ alkyl; or hydrogen.
 8. A process according to claim 7, wherein R₂and R₃ are each independently acyl; alkoxycarbonyl; nitro; cyano;arylsulphonyl; carbamoyl; haloalkyl; hydrogen; or C₁-C₄ alkyl.
 9. Aprocess according to claim 8, wherein R₂ and R₃ are each independentlyacetyl, ethylcarbonyl, phenylcarbonyl, methoxycarbonyl, ethoxycarbonyl,phenylsulphonyl, carbamoyl, N-ethylcarbamoyl, trifluoromethyl, methyl orethyl.
 10. A process according to claim 1, wherein: R₂ is cyano,hydrogen, methyl, or phenyl; and R₃ is alkoxycarbonyl, aryloxycarbonyl;hydrogen; methyl; or cyano.
 11. A process according to claim 10, whereinR₃ is methoxycarbonyl or ethoxycarbonyl.
 12. A process according toclaim 1, wherein R₄, R₆ and R₇ are each independently a linear orbranched C₁-C₄ alkyl radical; aryl; phenyl substituted by a halogen, amethoxy radical, a nitro group, a cyano group, a trifluoromethyl group,or an amino group; cyano; nitro; acylamino; arylamino; alkylthio;arylthio; carbamoyl; sulphonyl; alkoxycarbonyl; aryloxycarbonyl; acyl;or hydrogen.
 13. A process according to claim 12, wherein R₄, R₆ and R₇are each independently hydrogen; linear or branched C₁-C₄ alkyl; aryl;or phenyl substituted by a halogen, a methoxy radical, a nitro group, acyano group, a trifluoromethyl group, or an amino group.
 14. A processaccording to claim 13, wherein R₄, R₆, and R₇ are each independentlymethyl, ethyl, isopropyl, or phenyl.
 15. A process according to claim 1,wherein R₅ is acyl; alkoxycarbonyl; aryloxycarbonyl; nitro; cyano;arylsulphonyl; haloalkyl; or hydrogen.
 16. A process according to claim15, wherein R₅ is cyano; alkoxycarbonyl; aryloxycarbonyl; haloalkyl; orhydrogen.
 17. A process according to claim 16, wherein R₅ ismethoxycarbonyl, ethoxycarbonyl, or trifluoromenthyl.
 18. A processaccording to claim 1, wherein said coupler is: (i) apyrrolo[1,2-b]-1,2,4-triazole of formula (Ia):

or (ii) a pyrrolo[2,1-c]-1,2,4-triazole of formula (Ib):

wherein R₁, R₂, R₃, and R₄ are as defined in claim 1; or an acidaddition salt thereof.
 19. A process according to claim 18, wherein saidcoupler is a pyrrolo[1,2-b]-1,2,4-triazole of formula (Ia), wherein: R₁is hydrogen or chlorine; R₂ and R₃ are, respectively: cyano and cyano;ethoxycarbonyl and cyano; trifluoromethyl and cyano; phenylsulphonyl andcyano; trifluoromethyl and ethoxycarbonyl; ethoxycarbonyl andethoxycarbonyl; methoxycarbonyl and methoxycarbonyl; hydrogen andhydrogen; or hydrogen and methyl; and R₄ is methyl, ethyl, isopropyl,phenyl or hydrogen.
 20. A process according to claim 18, wherein saidcoupler is a pyrrolo[1,2-b]-1,2,4-triazole of formula (Ia), wherein: R₁is hydrogen or chlorine; R₂ and R₃ are simultaneously cyano or hydrogen;and R₄ is methyl, ethyl, isopropyl, phenyl, or hydrogen.
 21. A processaccording to claim 18, wherein said coupler is:3,4-dicyano-8-methylpyrrolo[1,2-b]-1,2,4-triazole,3,4-dicyano-8-phenylpyrrolo[1,2-b]-1,2,4-triazole,3,4-dicyano-8-tert-butylpyrrolo[1,2-b]-1,2,4-triazole, or5-Chloro-3,4-dicyano-8-methylpyrrolo[1,2-b]-1,2,4-triazole, or an acidaddition salt thereof.
 22. A process according to claim 18, wherein saidcoupler is a pyrrolo[2,1-C]-1,2,4-triazole of formula (Ib) wherein: R₁is hydrogen or chlorine; R₂ and R₃ are simultaneously cyano or hydrogen;and R₄ is methyl, ethyl, isopropyl, phenyl, or hydrogen.
 23. A processaccording to claim 18, wherein coupler is:5,6-dicyano-3-methylpyrrolo[2,1-c]-1,2,4-triazole, or7-chloro-5,6-dicyano-3-methylpyrrolo[2,1-c]-1,2,4-triazole, or anaddition salt thereof.
 24. A process according to claim 1, wherein saidcoupler is: a) a pyrrolo[1,2-b]-1,2,4-triazole of formula (IIa):

b) a pyrrolo[2,1-c]-1,2,4-triazole of formula (IIb):

c) a pyrrolo[1,2-c]imidazole of formula (IIc):

d) a pyrrolo[1,2-e]tetrazole of formula (IId):

e) a pyrrolo[1,2-a]pyrrole of formula (IIe):

f) a pyrrolo[1,2-a]imidazole of formula (IIf):

or g) a pyrrolo[1,2-c]-1,2,3-triazole of formula (IIg):

wherein R₁, R₂, R₃, R₄, R₅, R₆, and R₇ are as defined in claim
 1. 25. Aprocess according to claim 24, wherein said coupler is apyrrolo[1,2-b]-1,2,4-triazole of formula (IIa), wherein: R₁ is hydrogenor chlorine; R₂ and R₃ are, respectively: methoxycarbonyl and cyano;ethoxycarbonyl and cyano; cyano and methoxycarbonyl or ethoxycarbonyl;cyano and trifluoromethyl; cyano and phenylsulphonyl; methoxycarbonyland methoxycarbonyl; hydrogen and hydrogen; hydrogen and methyl;trifluoromethyl and cyano or trifluoromethyl and methoxycarbonyl;carboxyl and cyano; cyano and cyano; ethoxycarbonyl and ethoxycarbonyl;phenyl and cyano; or methyl and hydrogen; and R₄ is methyl, ethyl,isopropyl, phenyl or hydrogen.
 26. A process according to claim 25,wherein said coupler is:5-cyano-4-ethoxycarbonyl-8-methylpyrrolo[1,2-b]-1,2,4-triazole,5-cyano-4-carboxy-8-methylpyrrolo[1,2-b]-1,2,4-triazole,4,5-dicyano-8-methylpyrrolo[1,2-b]-1,2,4-triazole,5-cyano-8-methyl-4-phenylpyrrolo[1,2-b]-1,2,4-triazole,4,8-dimethylpyrrolo[1,2-b]-1,2,4-triazole,4,5-di(ethyloxycarbonyl)-8-methylpyrrolo[1,2-b]-1,2,4-triazole,3-chloro-5-cyano-4-ethoxycarbonyl-8-methylpyrrolo[1,2-b]-1,2,4-triazole,5-cyano-4-ethoxycarbonyl-8-phenylpyrrolo[1,2-b]-1,2,4-triazole,5-cyano-4-carboxy-8-phenylpyrrolo[1,2b]-1,2,4-triazole,4,5-dicyano-8-phenylpyrrolo[1,2-b]-1,2,4-triazole,4,5-di(ethyloxycarbonyl)-8-phenylpyrrolo[1,2-b]-1,2,4-triazole,3-chloro-5-cyano-4-ethoxycarbonyl-8-phenylpyrrolo[1,2-b]-1,2,4-triazole,or4-cyano-5-carboxy-8-(2-nitro-5-hydroxyphenyl)pyrrolo[1,2-b]-1,2,4-triazole,or an acid addition salt thereof.
 27. A process according to claim 24,wherein said coupler is a pyrrolo[2,1-c]-1,2,4-triazole of formula(IIb), wherein: R₁ is hydrogen or chlorine; R₂ and R₃ are, respectively:cyano and methoxycarbonyl; methoxycarbonyl and cyano; methoxycarbonyland methoxycarbonyl; hydrogen and hydrogen or hydrogen and methyl; cyanoand cyano; ethoxycarbonyl and ethoxycarbonyl; phenyl and cyano; ortert-butyl and cyano; and R₄ is methyl, ethyl, isopropyl, phenyl orhydrogen.
 28. A process according to claim 27, wherein said coupler is:6,7-dicyano-3-methylpyrrolo[2,1-c]-1,2,4-triazole,5-chloro-6,7-dicyano-3-methylpyrrolo[2,1-c]-1,2,4-triazole,6,7-di(ethyloxycarbonyl)-3-methylpyrrolo[2,1-c]-1,2,4-triazole,7-cyano-3-methyl-6-phenylpyrrolo[2,1-c]-1,2,4-triazole, or7-cyano-3-methyl-6-tert-butylpyrrolo[2,1-c]-1,2,4-triazole, or an acidaddition salt thereof.
 29. A process according to claim 24, wherein saidcoupler is a pyrrolo[1,2-c]imidazole of formula (IIc), wherein: R₁ isacetamido, chlorine or hydrogen; R₂ and R₃ are, respectively,methoxycarbonyl and cyano; or cyano and cyano; R₄ is hydrogen; and R₅ iscyano.
 30. A process according to claim 29, wherein said coupler is:6,8-dicyano-5-ethoxycarbonylpyrrolo[1,2-c]imidazole, or4-chloro-6,8-dicyano-5-ethoxycarbonylpyrrolo[1,2-c]imidazole, or an acidaddition salt thereof.
 31. A process according to claim 24, wherein saidcoupler is a pyrrolo[1,2-e]tetrazole of formula (IId): R₁ is hydrogen orchlorine; and R₂ and R₃ are, respectively: cyano and methoxycarbonyl;cyano and cyano; methoxycarbonyl and cyano; methoxycarbonyl andmethoxycarbonyl; hydrogen and hydrogen; or hydrogen and methyl.
 32. Aprocess according to claim 31, wherein said coupler is:6,7-dicyanopyrrolo[1,2-e]tetrazole,6-cyano-7-ethoxycarbonylpyrrolo[1,2-e]tetrazole,5-chloro-6,7-dicyanopyrrolo[1,2-e]tetrazole, or an acid addition saltthereof.
 33. A process according to claim 24, wherein said coupler is apyrrolo[1,2-a]pyrrole of formula (IIe), wherein: R₁ is hydrogen orchlorine; R₂ and R₃ are, respectively, cyano and methoxycarbonyl; R₅ istrifluoromethyl; R₆ is phenyl or methyl; and R₇ is methyl.
 34. A processaccording to claim 24, wherein said coupler is a pyrrolo[1,2-a]imidazoleof formula (IIf), wherein: R₁ is hydrogen or chlorine; and R₂, R₃, R₆and R₇ are, respectively: methoxycarbonyl, cyano, cyano, and phenyl;cyano, methoxycarbonyl, cyano, and phenyl; cyano, methoxycarbonyl,methoxycarbonyl, and phenyl; hydrogen, hydrogen, hydrogen, and hydrogen;or hydrogen, hydrogen, methyl, and methyl.
 35. A process according toclaim 34, wherein said coupler is:2,3,7-tricyano-6-methylpyrrolo[1,2-a]imidazole,2,3,7-tricyano-6-trifluoromethylpyrrolo[1,2-a]imidazole,2,3,7-tricyano-6-tert-butylpyrrolo[1,2-a]imidazole,2,3,7-tricyano-6-phenylpyrrolo[1,2-a]imidazole,2,3,7-tricyano-6-ethoxycarbonylpyrrolo[1,2-a]imidazole,5-chloro-2,3,7-tricyano-6-tert-butylpyrrolo[1,2-a]imidazole,5-chloro-2,3,7-tricyano-6-phenylpyrrolo[1,2-a]imidazole,7-cyano-6-ethoxycarbonylpyrrolo[1,2-a]benzimidazole,7-cyano-6-phenylpyrrolo[1,2-a]benzimidazole,7-amido-6-ethoxycarbonylpyrrolo[1,2-a]benzimidazole, or an acid additionsalt thereof.
 36. A process according to claim 24, wherein said coupleris a pyrrolo[1,2-c]-1,2,3-triazole of formula (IIg), wherein: R₁ ishydrogen or chlorine; R₂ is cyano; R₃ is methoxycarbonyl orethoxycarbonyl; and R₅ is cyano.
 37. A process according to claim 36,wherein said coupler is: 5,6,8-tricyanopyrrolo[1,2-c]-1,2,3-triazole,5,8-dicyano-6-ethoxycarbonylpyrrolo[1,2-c]-1,2,3-triazole, or4-chloro-5,8-dicyano-6-ethoxycarbonylpyrrolo[1,2-c]-1,2,3-triazole, oran acid addition salt thereof.
 38. A process according to claim 1,wherein said coupler is a hydrochloride, hydrobromide, tartrate,tosylate, benzenesulphonate, sulphate, lactate, or acetate acid additionsalt.
 39. A process according to claim 1, wherein said at least onepyrrolo-azole compound is present in an amount ranging from about 0.0005to about 12% by weight relative to the total weight of said composition.40. A process according to claim 39 wherein said at least onepyrrolo-azole compound is present in an amount ranging from about 0.005to about 6% by weight relative to the total weight of said composition.41. A process according to claim 1, wherein said at least one oxidationbase is present in an amount ranging from about 0.0005 to about 12% byweight relative to the total weight of said composition.
 42. A processaccording to claim 41, wherein said at least one oxidation base ispresent in an amount ranging from about 0.005 to about 6% by weightrelative to the total weight of said composition.
 43. A processaccording to claim 1, wherein said composition further comprises atleast one additional coupler other than said at least one pyrrolo-azolecompound of formula (I) or formula (II), at least one direct dye, or atleast one of each.
 44. A process according to claim 43, wherein said atleast one additional coupler is present in an amount ranging from about0.0005 to about 5% by weight relative to the total weight of saidcomposition.
 45. A process according to claim 44, wherein said secondcoupler is present in an amount ranging from about 0.005 to about 3% byweight relative to the total weight of said composition.
 46. A processaccording to claim 1, wherein said medium suitable for dyeing compriseswater or water and an organic solvent.
 47. A process according to claim46, wherein said medium suitable for dyeing comprises water and anorganic solvent which is a C₁-C₄ lower alkanol, glycerol, glycol, glycolether, an aromatic alcohol, or a mixture thereof.
 48. A processaccording to claim 47, wherein said organic solvent is present in anamount ranging from about 1 to about 40% by weight relative to the totalweight of said composition.
 49. A process according to claim 48, whereinsaid organic solvent is present in an amount ranging from about 5 toabout 30% by weight relative to the total weight of said composition.50. A process according to claim 1, wherein said composition has a pHranging from about 3 to about
 12. 51. A process according to claim 1,wherein said composition is in the form of a liquid, cream, or gel. 52.A process according to claim 1, wherein said at least one oxidizingagent is hydrogen peroxide, urea peroxide, an alkali metal bromate, or apersalt.
 53. A process according to claim 52, wherein said at least oneoxidizing agent is a persalt, and further wherein said persalt is aperborate or persulphate.
 54. A process according to claim 52, whereinsaid at least one oxidizing agent is hydrogen peroxide.
 55. A processaccording to claim 1, further comprising mixing at the time ofapplication and before said applying step, said at least one dyeingcomposition with an oxidizing composition comprising, in a mediumsuitable for dyeing, at least one oxidizing agent in an amountsufficient to develop coloration; and after said developing step,leaving said mixture on said keratin fibers for a time ranging fromabout 3 to about 50 minutes; then rinsing, washing, rinsing again anddrying said keratin fibers.
 56. A process according to claim 55, whereinsaid time ranges from about 5 to about 30 minutes.
 57. A processaccording to claim 1, wherein the oxidation base is a hydrochloride,hydrobromide, sulphate, tartrate, lactate, or acetate acid additionsalt.
 58. A process according to claim 43, wherein said at least oneadditional coupler is a hydrochloride, hydrobromide, sulphate, tartrate,lactate, or acetate acid addition salt.
 59. A process according to claim1, wherein said at least one oxidation base is chosen from apara-phenylenediamine, a bis(phenyl)alkylenediamine, a para-aminophenol,an ortho-aminophenol, a heterocyclic base, and an acid addition saltthereof.
 60. A process according to claim 59, wherein saidpara-phenylenediamine is a compound of formula (III) or an acid additionsalt thereof:

in which: R₈ is chosen from a hydrogen atom, a C₁-C₄ alkyl radical, aC₁-C₄ monohydroxyalkyl radical, a C₂-C₄ polyhydroxyalkyl radical, and a(C₁-C₄) alkoxy (C₁-C₄) alkyl radical; R₉ is chosen from a hydrogen atom,a C₁-C₄ alkyl radical, a C₁-C₄ monohydroxylalkyl radical, and a C₂-C₄polyhydroxyalkyl radical; R₁₀ is chosen from a hydrogen atom, a halogenatom, a C₁-C₄ alkyl radical, a sulpho group, a carboxyl radical, a C₁-C₄monohydroxylalkyl radical, and a C₁-C₄ hydroxyalkoxy radical; and, R₁₁is chosen from a hydrogen atom and a C₁-C₄ alkyl radical.